Preparation Of Nanoporous Composites Based On MOFs Derivatization And Its Application In Analytical Detection

Nanoporous materials are the hot spot of research on new nanomaterials.Mainly because the nanoporous material has a simple preparation method,easy to optimize the structure,the large specific surface area,the ordering porous,the better adsorption performance and etc.Therefore,the research fields of nanoporous materials are growing rapidly,which promotes the application of nanomaterials in other emerging fields,such as energy storage,gas separation,biosensors,nanocatalysis,drug delivery and fuel cell technology.Among them,MOFs and their derivatives are easy to ion exchange,have many metal active sites,good material stability,and large specific surface area.They have made important achievements in biosensing and detection,imaging,and disease treatment.Therefore,MOFs nanomaterials have important application prospects in the future.Therefore,this paper is based on the previous research and innovation,we studied the preparation of the following nanoporous materials and its application in biological detection.First,MOF-5-L as a precursor and template,Copper acetate as a second precursor forms layered Cu HDSs nanoflowers and is applied to a label-free glucose colorimetric detection platform.The second is to prepare Eu HDSs nanoflower probe,which is based on the anion exchange luminescence inhibition mechanism with high sensitivity and high selectivity for fluorescence detection of ascorbic acid.The third is to prepare water-soluble Invertase@ZIF-8@CMC nanomaterials,and use a blood glucose meter to detect the concentration of glucose in the organism by invertase hydrolysis of sucrose to achieve early diagnosis of cancer cells.This dissertation is divided into four chapters,which are briefly described as follows:Chapter 1:We briefly describe the concept and classification of nanoporous materials,including organometallic framework materials(MOFs)and hydrotalcite materials,as well as their current application areas.Chapter 2:This work reports for the first time that MOF-5-L is used as a precursor,template and copper acetate as a second precursor to form layered Cu-hydroxy complex salts(HDSs)and apply them to label-free glucose colorimetric detection.We provide a simple method for the simple synthesis of Cu HDSs nanoflowers with controlled morphology.Density functional theory(DFT)calculations confirmed the presence of a hydrogen bond between the terephthalate anion and the OH group between the layers.Experimental results show that the composition of Cu HDSs is[Cu4(OH)6][BDC]·2H2O.Importantly,the prepared Cu HDSs were first demonstrated to be peroxidase mimics,and in the presence of H2O2,the substrate developer 3’,3’,5,5’-tetramethyl Benzidine(TMB)changed from colorless to blue and followed the classical Michaelis-Menten equation.Based on the above findings,the colorimetric method based on Cu HDSs was developed,which has high sensitivity and selectivity for glucose detection with a detection limit as low as 0.5μM.In addition,we have demonstrated the clinical applicability of this sensor is suitable for glucose detection in the blood,indicating that Cu HDSs can be used to construct glucose portable sensors in the blood for immediate diagnosis and field testing.Chapter 3:This work prepares this Eu HDSs by using the leaf metal-organic framework-5(MOF-5-L)as the precursor and template and the ruthenium(Ⅲ)trihydrate trihydrate as the second precursor.In this work,the Eu HDSs nanoflower material was first characterized,and then the material was studied based on the anion exchange-based luminescence inhibition mechanism,which is quite different from the reported redox-based fluorescence sensing system.This fluorescent nanoprobe has high selectivity and excellent sensitivity for AA detection,and the experimental detection limit is as low as 1.46 nM.In addition,such luminescent nanoprobes have been successfully used to detect AA in human body fluids.Studies have shown that the sensors proposed in this work have great potential for clinical diagnosis and drug screening.Chapter 4:In this work,we first use a one-pot biomimetic mineralization to form Invertase@ZIF-8,and then modify it by carboxymethyl cellulose to change the "water solu bility" of ZIF-8 material,so we prep are materials with good biocompatibility.Finally,we use a blood glucose meter to detect the organism’s hydrolysis of sucrose by sucrase to produce glucose,thus achieving early cdiagnosis of cancer cells.Im portantly,this is the first time that CMC has been used to alter the stability and water solubility of ZIF-8 and to apply its materials to ea rly diagnosis of cancer cells.Based on the above findings,we have demonstrated that this research method is suitable for the detection of cancer cells,and th us achieve early diagnosis of cancer.